CN114044587B - Manganese oxide film loaded expanded bed filter and method for removing thallium by adsorption by using same - Google Patents
Manganese oxide film loaded expanded bed filter and method for removing thallium by adsorption by using same Download PDFInfo
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- CN114044587B CN114044587B CN202111372534.3A CN202111372534A CN114044587B CN 114044587 B CN114044587 B CN 114044587B CN 202111372534 A CN202111372534 A CN 202111372534A CN 114044587 B CN114044587 B CN 114044587B
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 182
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 110
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 238
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 55
- 230000007704 transition Effects 0.000 claims abstract description 37
- 238000007667 floating Methods 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 235000020188 drinking water Nutrition 0.000 claims abstract description 16
- 239000003651 drinking water Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 238000011010 flushing procedure Methods 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000008213 purified water Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011150 reinforced concrete Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000004576 sand Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000002349 well water Substances 0.000 description 4
- 235000020681 well water Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/11—Turbidity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a manganese oxide film-loaded expanded bed filter and a method for removing thallium in water by applying the same; the manganese oxide film loaded expansion bed filter comprises a filter body, a water collecting tank, an upper transition zone, a filter screen plate, a manganese oxide film loaded expansion filter bed, a lower transition zone and a water collecting device which are sequentially contained in the filter body from top to bottom, wherein the manganese oxide film loaded expansion filter bed is formed by loading MnO on the surface 2 The density of water-immersed particles of the oxide film is 0.95+/-0.5 g/cm 3 The floating ceramsite is uniformly laid; the water inlet pipe is provided with KMnO 4 And a solution feeding port. The invention passes MnO 4 ﹣ Reduction and Mn 2+ Oxidation to produce great amount of nascent state MnO 2 The manganese oxide film is slowly thickened along with the continuous addition of the potassium permanganate and adsorbed on the surface of the ceramsite, and the adsorption thallium is not saturated and does not need to be regenerated. The method can control the thallium concentration of the effluent to stably reach the standard of the drinking water with the concentration of < 0.1 mug/L.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a manganese oxide film loaded expanded bed filter and a thallium removing adsorption method using the same.
Background
Thallium is a rare-earth element and is often associated with mineral deposits such as pyrite and galena. The monovalent thallium has strong migration activity, and the toxicity of trivalent thallium is thousands times higher than that of monovalent thallium. Thallium content in natural water is generally low, lake is 0.001-0.4 mug/L, river is 0.01-1.35 mug/L, and groundwater is 0.001-0.85 mug/L. The thallium-containing ore deposit in China has rich resources and wide distribution, thallium-polluted water sources also appear along with the resources, and pollution events caused by thallium-containing wastewater in ore areas occur sometimes.
At present, the thallium standard in drinking water required to be living in China is less than or equal to 0.1 mug/L. In some areas where geological conditions contain thallium, well water and even reservoir water as a source of drinking water may have the problem that the thallium content in raw water exceeds standards. For monovalent thallium, the existing tap water purification process, including ultrafiltration membrane process, cannot effectively remove thallium to realize standard water supply. Under the condition that a water source is polluted by thallium, the most effective method at present is to throw potassium permanganate into the water inlet end of a waterworks with a sand filter, and remove part of thallium through the sand filter. The thallium removal is actually achieved by sand filter adsorption. As the thickness of the sand filter is only about 1m, and the iron-manganese oxide film attached to the surface is not more, the adsorption capacity is limited, the sand filter is easy to penetrate, and the thallium content of raw water exceeds 0.15 mug/L after the treatment by the technology is difficult to reach the standard. In addition, as the raw water contains more reducing substances, the consumption of potassium permanganate is greatly increased, and in order to avoid the red color of the effluent, the addition amount of the potassium permanganate is restricted, and the thallium removal effect is also affected. More risky, most thallium adsorbed by the technology stays in the sand filter, so that the sand filter becomes a new thallium pollution source, and once the potassium permanganate dosage is reduced, the thallium adsorbed in the sand filter can be influenced by Mn in water 2+ And Fe (Fe) 2+ Cations which are easy to be adsorbed by the sand filter are exchanged and separated out into filtered water in a large quantity, and the superscalar times are often times that of the thallium-containing raw water. Therefore, the tap water thallium removal method for removing thallium by means of a sand filter by adopting the front potassium permanganate has great disadvantages.
At present, the most stringent emission limit formulated for thallium-containing industrial wastewater in China is less than or equal to 2 mug/L, which is 20 times of the standard of domestic drinking water. The determination of industrial wastewater discharge limits is mainly limited by thallium removal methods and costs. At present, the thallium removal method by adopting an adsorption material is adopted for purifying thallium-containing industrial wastewater, and the operation is maintained through regeneration, so that the thallium-containing wastewater can be stably up to less than or equal to 2 mug/L.
Chinese patent 201110231227.3 discloses a method for removing thallium pollution from source water of drinking water, comprising the following steps: a. adjusting the pH value to 9.0-9.5 when the thallium pollution concentration is not higher than 1 mug/L; when the thallium pollution concentration is 1-5 mug/L, the pH value is adjusted to 9.510.0; b. pre-oxidizing, using potassium permanganate as pre-oxidizing agent of thallium to make Tl + Conversion to Tl 3+ Adding 1.5-2.5mg/L potassium permanganate, and oxidizing for 20-40min; c. coagulating sedimentation, adding polyaluminium chloride to make Tl 3+ Tl (OH) 3 precipitate is formed and thallium in the source water is removed by filtration. However, this technique requires adjustment of pH, and the added polyaluminum chloride cannot be reused, and water treatment costs are high.
Disclosure of Invention
The invention aims at overcoming the defects of the prior adsorption thallium removal technology, provides a manganese oxide loaded membrane expanded bed filter and a method for removing thallium by using the same, which are suitable for treating various thallium-containing wastewater, in particular for thallium-containing water source and drinking water supply systems, and the thallium concentration can be stably reduced to a level of less than 0.1 mug/L, thereby conforming to the sanitary standard of domestic drinking water 2 The oxide film can be reused, only a certain amount of potassium permanganate is needed to be added, and the treatment cost is low.
The floating ceramsite is oxidized by potassium permanganate, and a layer of MnO is loaded on the surface of the floating ceramsite 2 And then, taking the ceramsite loaded with the manganese oxide film as a filter material, and cooperatively adding potassium permanganate after the raw water is subjected to turbidity removal. Oxidation film on surface of filter material for Mn in water 2+ 、MnO 2 、MnO 4 ﹣ And Fe (Fe) 2+ Has strong adsorption effect on MnO 4 ﹣ Oxidation of Mn 2+ And Fe (Fe) 2+ Has strong catalytic action by MnO 4 ﹣ Reduction and Mn 2+ Oxidation can rapidly generate a large amount of nascent state MnO 2 Is adsorbed on the surface of the floating ceramsite. New ecological MnO 2 The thallium is efficiently adsorbed and removed by ion exchange of the surface complexing hydroxyl group and thallium. Ecological MnO 2 After thallium adsorption, the thallium continues to adhere to the oxide film to form a new manganese film layer. Along with the continuous addition of potassium permanganate, the manganese oxide film is continuously thickened, and adsorption thallium removal is not saturated and does not need regeneration; the potassium permanganate is added in a certain amount by MnO 4 ﹣ Oxidation promoting growth of enough amount of nascent state MnO 2 Satisfies the requirement of adsorption thallium removalThe requirement is that Mn in water can be removed by sufficient oxidation 2+ And Fe (Fe) 2+ The adsorbed thallium is prevented from being exchanged and precipitated, and the thallium removal efficiency is improved. The turbidity removal pretreatment of raw water can reduce the interference of turbidity substances on nascent state MnO 2 Implantation, the phenomenon that thallium removal efficiency is affected by frequent flushing and increased demolding of filter materials is avoided. The purpose of adopting the floating ceramsite to load the manganese oxide film is to have the advantages of small water loss, low operation energy consumption, simple flushing mode and easy maintenance and management by means of the expanded bed filter tank.
The invention aims at realizing the following technical scheme:
the manganese oxide film loaded expanded bed filter comprises a filter body, a water collecting tank, an upper transition area, a filter screen plate, a manganese oxide film loaded expanded filter bed, a lower transition area and a water collecting device which are sequentially arranged in the filter body from top to bottom, wherein a water inlet pipe is communicated with the water distributing tank or the bottom water collecting device; the manganese oxide film loaded expansion filter bed is prepared by loading MnO on the surface 2 The density of water-immersed particles of the oxide film is 0.95+/-0.5 g/cm 3 The floating ceramsite is uniformly laid; the water inlet pipe is provided with KMnO 4 And a solution feeding port.
To further achieve the object of the present invention, preferably, the expanded filter bed supported manganese oxide film is prepared by the following method: mn is added to 2+ Adding potassium permanganate into the aqueous solution with the concentration of more than 0.3mg/L, and then pumping the aqueous solution into a coating tank for placing floating ceramsite, wherein the concentration of the potassium permanganate in water is controlled to be 0.4-1mg/L; under the catalysis of the gradually generated manganese oxide film, the manganese oxide film passes through MnO 4 ﹣ Is reduced and Mn of 2+ Is oxidized to rapidly generate a large amount of MnO 2 Is adsorbed on the surface of the floating ceramsite.
Preferably, the floating ceramsite is prepared by the following method: shale is taken as raw material, crushed and dried by a crusher, burned in a rotary kiln for 18-22 min, the burning temperature is controlled to be 1100-1300 ℃, naturally cooled after discharging, crushed, screened and selected to obtain ceramsite with the grain diameter of 5-12 mm, and the density of water-immersed grains is 0.95+/-0.5 g/cm 3 Is a floating ceramsite.
Preferably, the gas flushing pipe of the manganese oxide loaded expanded bed filter is communicated with the bottom gas distribution device; the flushing wastewater drain pipe is communicated with a water collecting main pipe of the bottom water collecting device; the other end of the air flushing pipe is connected with a blower.
The manganese oxide film loaded expansion bed filter is a down-flow filter or an up-flow filter; for the down-flow filter, a water inlet pipe is communicated with a water distribution tank, and a water outlet pipe is communicated with a water collecting main pipe of a bottom water collecting device; for the upflow filter, the water inlet pipe is communicated with the water collecting main pipe of the bottom water collecting device, and the water outlet pipe is communicated with the water distributing groove.
Preferably, the horizontal section of the filter body is rectangular or circular.
Preferably, when the filter body adopts a reinforced concrete structure, the horizontal cross section of the filter body is rectangular; when the filter tank body is welded by steel plates, the horizontal section of the filter tank body is round or rectangular.
Preferably, the mesh diameter of the filter screen plate is 3-5 mm; the filter screen plate is made of stainless steel;
the upper transition area is a space between the water distribution groove and the filter screen plate, and the height of the upper transition area is 0.3-1 m;
the lower transition zone is the space between the lower part of the manganese oxide film-loaded expanded filter bed and the bottom water collecting device, and the height of the lower transition zone is 0.3-1 m.
The manganese oxide film loaded expanded bed filter further comprises a bottom gas distribution device, wherein the bottom gas distribution device is positioned in the lower transition zone and consists of a gas distribution main pipe and a plurality of perforated gas pipes; the perforated air pipe is horizontally arranged above the pool bottom and is communicated with the air distribution main pipe;
the water collecting device consists of a water collecting main pipe and a plurality of perforated water pipes; the perforated water pipe is horizontally arranged above the pool bottom and connected with the water collecting main pipe.
Preferably, the water inlet pipe, the water outlet pipe, the gas flushing pipe and the flushing wastewater drainage pipe are all provided with valves.
The method for removing thallium by adsorption by using the manganese oxide loaded expanded bed filter comprises the following steps: if the overflow mode adopts a down-flow mode, raw water added with potassium permanganate enters a water distribution tank from a water inlet pipe, overflows and is matched with an upper transition zone, is gradually and uniformly distributed to the whole filtering surface, flows downwards to penetrate through a filtering screen plate to enter a floating ceramsite filter bed, and after thallium is removed by adsorption of the floating ceramsite filter bed, purified water flows downwards to the lower transition zone and is collected to a water outlet pipe through a water collecting device to flow out;
if the overflow mode adopts up-flow, the raw water added with potassium permanganate enters the water collecting device from the water inlet pipe, is gradually and uniformly distributed to the whole filtering surface after being matched with the lower transition zone, flows upwards to enter the floating ceramsite filtering bed, passes through the floating ceramsite filtering bed to adsorb thallium, and then the purified water upwards passes through the filtering screen plate to flow through the upper transition zone and is collected to the water outlet pipe through the water distribution tank to flow out.
Preferably, when the raw water is the drinking water containing thallium, the potassium permanganate dosage is controlled according to the potassium permanganate concentration of 0.3-0.5 mg/L in the water; for water with turbidity, the raw water is pretreated by turbidity removal and then potassium permanganate is added, and the potassium permanganate addition amount is controlled according to the potassium permanganate concentration of 0.3-0.5 mg/L in the water.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) The adsorption and thallium removal efficiency of the turbid raw water by the synergistic addition of potassium permanganate to the manganese oxide loaded expanded bed filter tank is high, the method is suitable for treating various thallium-containing wastewater, and is particularly suitable for a water supply system adopting thallium-containing water sources, potassium permanganate is added to raw water, and under the catalysis of a manganese oxide film, the thallium is removed by MnO 4 ﹣ Reduction and Mn 2+ Oxidation to produce great amount of nascent state MnO 2 Adsorbed on the surface of haydite and nascent state MnO 2 The thallium is efficiently adsorbed and removed by the way of ion exchange between the surface complexing hydroxyl and thallium, and the thallium concentration of the effluent can be steadily reduced to the level of less than 0.1 mug/L.
2) Unlike available adsorption thallium eliminating material with manganese ore material, the present invention has potassium permanganate oxidizing treatment mode to load manganese oxide film onto the filtering material, so that proper filtering material may be selected based on water quality. The filtering tank based on the floating ceramsite expansion bed has the advantages of small filtering water loss, low running energy consumption, no hardening of the filtering bed, simple flushing mode and easy maintenance and management, so that the floating ceramsite is selected to be rich in Mn 2+ The potassium permanganate oxidation treatment is carried out in the clear water to lead the surface of the floating ceramsite to be loaded with the waterThe manganese oxide film is brown. The newly loaded manganese oxide film of the filter material only bears Mn adsorption in the initial operation stage 2+ 、Fe 2+ 、MnO 2 And MnO 4 ﹣ The manganese oxide film layer is not required to have wear resistance and thickness. Along with the continuous addition of potassium permanganate, the manganese oxide film is continuously and slowly thickened and updated.
3) Unlike the existing principle of oxidizing and removing thallium by adding potassium permanganate, the invention has two aims of cooperatively adding potassium permanganate: one is to make use of manganese oxide film to MnO 4 ﹣ Oxidation of Mn 2+ And Fe (Fe) 2+ Has strong catalytic action by MnO 4 ﹣ Is reduced and Mn of 2+ Oxidation of growth promoting amount of nascent state MnO 2 The thallium is removed by adsorption; secondly, mn is removed by full oxidation 2+ 、Fe 2+ So as to avoid the exchange precipitation of thallium adsorption and improve thallium removal efficiency. New ecological MnO continuously generated along with the synergistic addition of potassium permanganate 2 Thallium is adsorbed on the surface and then continuously attached to the oxide film to form a new manganese film layer. Along with the continuous addition of potassium permanganate, the manganese oxide film is continuously thickened, and adsorption thallium removal is not saturated, so that regeneration is not needed.
4) When the manganese oxide loaded expanded bed filter is operated, only potassium permanganate is needed, thallium removal efficiency is high, regeneration is not needed, filtering water loss of the membrane expanded bed filter is small, a filter bed is not hardened, a flushing mode is simple, operation energy consumption is low, maintenance and management are easy, and operation cost is low.
5) The pretreatment of removing turbidity is preferably carried out on raw water by adopting a manganese oxide loaded membrane expanded bed filter. The low turbidity of the inlet water is beneficial to maintaining the quality of the manganese oxide film, keeping the water flow fully contacted with the manganese oxide film, and avoiding MnO caused by frequent flushing of filter materials 2 Eluting to improve the thallium removal rate by adsorption.
6) For wastewater treatment, raw water still contains more organic matters after the turbidity removal pretreatment, and biological mud films are gradually covered on the surfaces of filter materials, so that the contact between manganese oxide films and water flow is weakened, and the filtration head loss of a filter tank is increased. Therefore, the filter tank needs to be backwashed regularly, and the strength and frequency of the backwashed are high, so that the water flow is kept in contact with the manganese oxide film, and the overflow capacity is recovered. The occasion is suitable for adopting the manganese oxide film-loaded expanded bed filter, and the particle density of the filter material is close to that of water, so that the filter material has small water loss, low operation energy consumption, simple flushing mode and easy maintenance and management.
7) For water supply treatment, the manganese oxide loaded expanded bed filter is suitable for taking water from the front of a clean water tank of a treatment system, the turbidity of raw water after turbidity removal pretreatment can be controlled below 3NTU generally, and the filter is often only required to be backwashed once at intervals of a plurality of weeks due to the very small organic matter content in the water, so that the configuration of air and water backwashing facilities is simpler. The manganese oxide film-loaded expanded bed filter can be adopted, so that the filter has small filtration water loss, low operation energy consumption and easy maintenance and management; the ceramsite loaded manganese oxide film with the particle density heavier than water can be used as a filter material, a filter screen plate is not required to be installed, and the construction cost of the filter is reduced.
Drawings
FIG. 1 is a schematic diagram of a down-flow structure of a manganese oxide loaded expanded bed filter of the present invention.
FIG. 2 is a schematic view of the upflow structure of the manganese oxide loaded expanded bed filter of the present invention.
FIG. 3 is a flow chart of a method for removing thallium by adsorption using a manganese oxide loaded expanded bed filter.
The figure shows: the filter tank body 1 of the expanded bed, the water distribution tank 2, the upper transition area 3, the filter screen plate 4, the expanded filter bed 5 of the loaded manganese oxide film, the lower transition area 6, the bottom gas distribution device 7, the bottom water collecting device 8, the water inlet pipe 9, the water outlet pipe 10, the gas flushing pipe 11 and the flushing wastewater drainage pipe 12.
Detailed Description
For a better understanding of the present invention, the following description is to be taken in conjunction with the accompanying drawings, and it should be noted that the present invention is not limited to the specific embodiments.
As shown in figures 1 and 2, the manganese oxide film loaded expanded bed filter comprises a filter body 1, a water distribution tank 2, an upper transition zone 3, a filter screen plate 4, a manganese oxide film loaded expanded filter bed 5, a lower transition zone 6 and a bottom water collecting container which are sequentially contained in the filter body from top to bottomSetting 8; the device also comprises a bottom gas distribution device 7, a water inlet pipe 9, a water outlet pipe 10, a gas flushing pipe 11 and a flushing wastewater drainage pipe 12, wherein various pipelines are respectively provided with valves for independently controlling the opening and the closing; the gas flushing pipe 11 is communicated with the bottom gas distribution device 7; the flushing wastewater drain pipe 12 is communicated with a water collecting main pipe of the bottom water collecting device 8; for the down-flow filter shown in fig. 1, a water inlet pipe 9 is communicated with a water distribution tank 2, and a water outlet pipe 10 is communicated with a water collecting main pipe of a bottom water collecting device 8; for the upflow filter shown in fig. 2, the water inlet pipe 9 is communicated with a water collecting main pipe of the bottom water collecting device 8, and the water outlet pipe 10 is communicated with the water distributing tank 2. The water inlet pipe 9 is provided with KMnO 4 Solution feed inlet for adding KMnO 4 A solution.
The manganese oxide film-loaded expansion filter bed 5 is loaded with MnO on the surface 2 The density of water-immersed particles of the oxide film is 0.95+/-0.5 g/cm 3 The floating ceramsite is uniformly paved to form. The floating ceramsite loaded manganese oxide film is prepared by the following method: mn is added to 2+ Adding potassium permanganate into the aqueous solution with the concentration of more than 0.3mg/L, pumping the aqueous solution into a coating tank for placing floating ceramsite, and controlling the concentration of the potassium permanganate to be 0.4-1mg/L. Under the catalysis of the gradually generated manganese oxide film, the manganese oxide film passes through MnO 4 ﹣ Is reduced and Mn of 2+ Can rapidly generate a large amount of nascent state MnO by oxidation 2 Adsorbing on the surface of floating haydite; the density of the water-immersed particles is 0.95+/-0.5 g/cm 3 The floating ceramsite is prepared by the following steps: shale is taken as raw material, crushed and dried by a crusher, burned in a rotary kiln for 18-22 min, the burning temperature is controlled to be 1100-1300 ℃, naturally cooled after being discharged, crushed by the crusher, and then screened, and the grain size is selected to be 5-12 mm, thus obtaining the water-immersed grain with the density of 0.95+/-0.5 g/cm 3 Is a floating ceramsite.
The invention uses MnO 4 ﹣ Reduction and Mn 2+ Oxidation to quickly generate nascent state MnO 2 Is adsorbed on the surface of the haydite to gradually form a tan manganese oxide film which is also suitable for MnO 4 ﹣ And Mn of 2+ The oxidation reaction of (2) plays a catalytic role to accelerate the generation of MnO 2 . The process is suitable for outdoor normal temperature, and when the floating ceramsite is loaded with manganese oxide filmAbout 1 to 2 weeks, with Mn in aqueous solution 2+ Concentration and potassium permanganate addition, mn 2+ The time consumption of film plating is shortened when the concentration and the potassium permanganate dosage are large.
The expansion bed filter can adopt a down-flow type or an up-flow type according to an overflow mode. The down-flow type water purifier is suitable for the occasion that the inlet water contains more suspended matters or easily-entangled and blocked pollutants, and the up-flow type water purifier is suitable for other occasions. The back flushing of the filter tank is facilitated by the down-flow type filter tank, but the water level of the filter tank changes along with the change of the water head loss of the filter tank; the upflow type filter has more strict limitation on impurities in water, and has the advantages of being beneficial to full contact between water flow and filter materials, and constant water level water outlet is beneficial to connection with follow-up.
The horizontal section of the filter body 1 is rectangular or shaped, and when a reinforced concrete structure is adopted, the horizontal section is preferably rectangular; when steel plate welding is used, it is preferably circular or rectangular.
The upper transition area 3 is a space between the water distribution tank 2 and the filter screen plate 4, preferably the height of the upper transition area is 0.3-1 m, and the upper transition area is used for forming uniform and excessive water flow between the water distribution tank and the whole filter surface;
the lower transition zone 6 is the space between the lower part of the manganese oxide-loaded expanded filter bed 5 and the water collecting device 8, and the height of the space is preferably 0.3-1 m, and the space is used for forming uniform and excessive water flow between the water collecting device and the whole filter surface. For the heavy ceramsite filter material filter tank, the lower transition area is a pebble cushion layer;
the filter screen plate 4 has the function of limiting the manganese oxide film loaded expansion filter bed 5 below the filter screen plate 4, so that the filter material is not lost through meshes of the filter screen plate 4, but the filter material does not block the flowing sewage. Preferably, the filter screen plate 4 is made of stainless steel, preferably, the mesh diameter is 3-5 mm, and the mesh diameter is more than 2mm smaller than the minimum size of the floating ceramsite;
the bottom gas distribution device 7 consists of a gas distribution main pipe and a plurality of perforated gas pipes. The perforated air pipe is horizontally arranged above the pool bottom and is communicated with the air distribution main pipe, the air distribution main pipe is communicated with the air flushing pipe 11, and the other end of the air flushing pipe 11 is connected with the air blower.
The bottom water collecting device 8 consists of a water collecting main pipe and a plurality of perforated water pipes; the perforated water pipe is horizontally arranged above the pool bottom and is connected with the water collecting main pipe, and the water collecting main pipe is communicated with the flushing wastewater drain pipe 12.
For the down-flow filter, a water inlet pipe 9 is communicated with a water distribution tank 2, and a water outlet pipe 10 is communicated with a water collecting main pipe of a bottom water collecting device 8; for the upflow filter, a water inlet pipe 9 is communicated with a water collecting main pipe of a bottom water collecting device 8, and a water outlet pipe 10 is communicated with a water distributing tank 2.
The water inlet pipe 9, the water outlet pipe 10, the gas flushing pipe 11 and the flushing wastewater drain pipe 12 are respectively provided with valves for controlling the opening and the closing independently.
The method for removing thallium by adsorption by using the manganese oxide loaded expanded bed filter tank comprises the following steps: the flow-through mode is shown in figure 1, raw water added with potassium permanganate enters the water distribution tank 2 from the water inlet pipe 9, overflows and is distributed into the upper transition zone 3, is gradually uniformly distributed to the whole filtering surface, and then flows downwards to penetrate through the filtering screen plate 4 to enter the manganese oxide loaded membrane expanded filtering bed 5. Because the floating ceramsite is slightly lighter than water, the filter bed is in a micro-expansion state under the pulsation of water flow. After thallium is removed by adsorption of the manganese oxide loaded membrane expanded filter bed 5, purified water flows downwards through the lower transition zone 6 and is collected to the water outlet pipe 10 by the bottom water collecting device 8 to flow out. The overflow mode adopts an up-flow mode, as shown in fig. 2, raw water added with potassium permanganate enters a bottom water collecting device 8 from a water inlet pipe 9, rises into a lower transition zone 6, is gradually and uniformly distributed to the whole filtering surface, flows upwards to enter a loaded manganese oxide membrane expanded filter bed 5, and passes through the loaded manganese oxide membrane expanded filter bed 5 to absorb thallium and then passes through a filter screen plate 4 upwards to flow through the upper transition zone 3, and is collected to a water outlet pipe 10 through a water distribution tank 2 to flow out.
If the filter of the expanded bed needs to be washed for a period of time, the water surface can be lowered to the net surface of the filter screen plate 4, the air blower is started, compressed air enters the bottom air distribution device 7 from the air flushing pipe 11 and is uniformly distributed to the whole pool surface and is diffused upwards, the manganese oxide loaded membrane expanded filter bed 5 is expanded and fluidized below the filter screen plate 4, the water discharging valve is started after a few minutes, and flushing wastewater is discharged out of the pool from the flushing wastewater discharging pipe 12.
For removing thallium from domestic drinking water, the filtration speed of the manganese oxide loaded expanded bed filter tank can be controlled to be 5-15 m/h, the potassium permanganate adding concentration is generally not more than 1.0mg/L, and the potassium permanganate adding concentration is more than 0.5mg/L, so that pink color of water can be possibly caused, and an activated carbon decolorization unit is required to be added if necessary. If the expanded bed filter tank needs to be washed, the water surface can be lowered to the surface of the filter screen, the blower is started, compressed air enters the bottom air distribution device from the backwashing air pipe and is uniformly distributed to the whole tank surface and is spread upwards, the ceramsite filter bed expands or even fluidizes below the filter screen, the drain valve is started after a few minutes, and the washing wastewater is discharged out of the tank from the washing wastewater drain pipe.
As shown in FIG. 3, the thallium-containing raw water is generally subjected to turbidity removal pretreatment, then potassium permanganate is added, and the thallium-containing raw water enters a manganese oxide loaded expanded bed filter to be adsorbed for thallium removal. For raw water with low turbidity, such as groundwater, etc., a turbidity removing pretreatment unit can be omitted, and the raw water directly enters a manganese oxide loaded membrane expanded bed filter to adsorb thallium. The low turbidity of the inlet water is beneficial to maintaining the quality of the manganese oxide film, keeping the water flow fully contacted with the manganese oxide film, and avoiding MnO caused by frequent flushing of filter materials 2 Eluting, improving the thallium removal rate by adsorption and reducing the addition amount of potassium permanganate. Quantitative potassium permanganate addition of raw water before entering an expanded bed filter tank is key for thallium removal, and one is nascent state MnO with growth promoting capacity 2 The thallium is removed by adsorption; secondly, mn is removed by full oxidation 2+ 、Fe 2+ So as to avoid the exchange precipitation of thallium adsorption, and if the dosage of potassium permanganate is insufficient, mn in water 2+ 、Fe 2+ Failure to remove the thallium sufficiently can cause massive exchange precipitation of thallium which has been adsorbed, resulting in serious exceeding of effluent.
Taking the village well water in Guangdong province as an example for thallium removal. The village adopts deep well water to supply domestic drinking water, the water pump is used for supplying water to a stainless steel clean water tank positioned on a hillside, and the water pump adopts water tank liquid level control to automatically run. The clear water tank water automatically flows into a village running water pipe and is connected to each user. The water supply amount of the water pump is 5-7 m 3 Per hour, the daily water supply is 80-150 m 3 . As a result of recent water quality detection, the thallium concentration in water is 0.25-0.45 mug/L, which exceeds the standard of sanitary drinking water by 1.5-3.2 times. In addition, the manganese concentration of the well water is 0.014-0.049 mg/L, and the iron concentration is<0.0045mg/L. At present, thallium removal of domestic drinking water adopts a water purification process of coagulation, precipitation and sand filtration, and is added before a coagulation unitPotassium permanganate, sodium hydroxide and flocculant. Under the condition that the thallium concentration of raw water exceeds 0.25mg/L, the thallium concentration of the discharged water is difficult to reach the sanitary standard of the drinking water which is less than 0.1 mug/L, the adopted process is complex, at least 3 kinds of medicaments such as potassium permanganate, sodium hydroxide, flocculating agent and the like are required to be added, frequent flushing is required, the management workload is increased, and the running cost is also greatly increased.
The method for removing thallium by adsorption by using a manganese oxide loaded membrane expanded bed filter is characterized in that the loading height of a manganese oxide loaded membrane expanded filter bed 5 in the membrane expanded bed filter is 2.5m, the empty bed filtering speed of the filter is 5-7 m/h after the membrane expanded bed filter is put into operation, the concentration of raw water after potassium permanganate is added is 0.35-0.45 mg/L, and the concentration of thallium in water outlet is detected to be 0.01-0.05 mug/L. For thallium removal of domestic drinking water, potassium permanganate addition concentration exceeding 0.5mg/L is likely to cause pink color of water, and active carbon needs to be added for decolorization if necessary. The method for removing thallium by adsorption by using the manganese oxide loaded expanded bed filter provided by the invention only needs to quantitatively add potassium permanganate, the expanded bed filter is not required to be washed for a long time, unattended operation is easy to realize, the operation cost is low, and the thallium concentration of the effluent can stably reach the standard of < 0.1 mug/L of domestic drinking water.
Claims (9)
1. The method for removing thallium by adsorption of the manganese oxide loaded expanded bed filter is characterized in that a down-flow mode is adopted in an overflow mode, raw water added with potassium permanganate enters a water distribution tank from a water inlet pipe, overflows and is matched with an upper transition area, is gradually and uniformly distributed to the whole filtering surface, flows downwards through a filtering screen plate to enter a manganese oxide loaded expanded bed, and after thallium is removed by adsorption of the manganese oxide loaded expanded bed, purified water flows downwards through a lower transition area and is collected to a water outlet pipe through a water collecting device to flow out;
the overflow mode adopts an up-flow mode, raw water added with potassium permanganate enters the water collecting device from the water inlet pipe, is gradually and uniformly distributed to the whole filtering surface after being matched with the lower transition zone, flows upwards to enter the manganese oxide film loaded expansion filtering bed, passes through the manganese oxide film loaded expansion filtering bed to absorb thallium, and purified water upwards passes through the filtering screen plate to flow through the upper transition zone and is collected to the water outlet pipe through the water distribution tank to flow out;
the manganese oxide film loaded expanded bed filter comprises a filter body, a water collecting tank, an upper transition area, a filter screen plate, a manganese oxide film loaded expanded filter bed, a lower transition area and a water collecting device which are sequentially arranged in the filter body from top to bottom, wherein a water inlet pipe is communicated with the water distributing tank or the bottom water collecting device; the manganese oxide film loaded expansion filter bed is prepared by loading MnO on the surface 2 The density of water-immersed particles of the oxide film is 0.95+/-0.5 g/cm 3 The floating ceramsite is uniformly laid; the water inlet pipe is provided with KMnO 4 A solution feed port;
the raw water entering from the down-flow and up-flow water inlet pipes is the drinking water containing thallium, and the potassium permanganate dosage is controlled according to the potassium permanganate concentration of 0.3-0.5 mg/L in the water.
2. The method for removing thallium by adsorption in a manganese-loaded oxide membrane expanded bed filter according to claim 1, wherein the surface is loaded with MnO 2 The density of water-immersed particles of the oxide film is 0.95+/-0.5 g/cm 3 The floating ceramsite is prepared by the following steps: mn is added to 2+ Adding potassium permanganate into the aqueous solution with the concentration of more than 0.3mg/L, and then pumping the aqueous solution into a coating tank for placing floating ceramsite, wherein the concentration of the potassium permanganate in water is controlled to be 0.4-1mg/L; under the catalysis of the gradually generated manganese oxide film, the manganese oxide film passes through MnO 4 ﹣ Is reduced and Mn of 2+ Is oxidized to rapidly generate a large amount of MnO 2 Is adsorbed on the surface of the floating ceramsite.
3. The method for removing thallium by adsorption in the manganese oxide loaded expanded bed filter according to claim 2, wherein the floating ceramsite is prepared by the following method: shale is taken as raw material, crushed and dried by a crusher, burned in a rotary kiln for 18-22 min, the burning temperature is controlled to be 1100-1300 ℃, naturally cooled after discharging, crushed, screened and selected to obtain ceramsite with the grain diameter of 5-12 mm, and the density of water-immersed grains is 0.95+/-0.5 g/cm 3 Is a floating ceramsite.
4. The method for removing thallium by adsorption in a manganese oxide loaded expanded bed filter according to claim 1, wherein a gas flushing pipe of the manganese oxide loaded expanded bed filter is communicated with a bottom gas distribution device; the flushing wastewater drain pipe is communicated with a water collecting main pipe of the bottom water collecting device; the other end of the air flushing pipe is connected with a blower;
the manganese oxide film loaded expansion bed filter is a down-flow filter or an up-flow filter; for the down-flow filter, a water inlet pipe is communicated with a water distribution tank, and a water outlet pipe is communicated with a water collecting main pipe of a bottom water collecting device; for the upflow filter, the water inlet pipe is communicated with the water collecting main pipe of the bottom water collecting device, and the water outlet pipe is communicated with the water distributing groove.
5. The method for removing thallium by adsorption in a manganese oxide loaded membrane expanded bed filter according to claim 1, wherein the horizontal cross section of the filter body is rectangular or circular.
6. The method for removing thallium by adsorption in a manganese oxide loaded membrane expanded bed filter according to claim 5, wherein when the filter body adopts a reinforced concrete structure, the horizontal cross-sectional shape of the filter body is rectangular; when the filter tank body is welded by steel plates, the horizontal section of the filter tank body is round or rectangular.
7. The method for removing thallium by adsorption in a manganese oxide loaded membrane expanded bed filter according to claim 1, wherein the mesh diameter of the filter screen plate is 3-5 mm; the filter screen plate is made of stainless steel;
the upper transition area is a space between the water distribution groove top and the filter screen plate, and the height of the upper transition area is 0.3-1 m;
the lower transition zone is a space between the lower part of the manganese oxide film loaded expansion filter bed and the bottom water collecting device, and the height of the lower transition zone is 0.3-1 m;
the manganese oxide film loaded expanded bed filter further comprises a bottom gas distribution device, wherein the bottom gas distribution device is positioned in the lower transition zone and consists of a gas distribution main pipe and a plurality of perforated gas pipes; the perforated air pipe is horizontally arranged above the pool bottom and is communicated with the air distribution main pipe;
the water collecting device consists of a water collecting main pipe and a plurality of perforated water pipes; the perforated water pipe is horizontally arranged above the pool bottom and connected with the water collecting main pipe.
8. The method for removing thallium by adsorption in a manganese oxide loaded expanded bed filter according to claim 7, wherein the water inlet pipe, the water outlet pipe, the gas flushing pipe and the flushing wastewater drainage pipe are all provided with valves.
9. The method for removing thallium by adsorption in a manganese oxide loaded membrane expanded bed filter according to claim 1, wherein the raw water is turbidity water, and potassium permanganate is added after the raw water is pretreated to remove turbidity.
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| 高锰酸钾与接触氧化协同除锰及硬度对除锰效果的影响;孙成超;杨海洋;梁恒;李圭白;;环境科学学报;40(10);第3674-3679页 * |
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